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Introduction

Encyclopædia Britannica, Inc.

Encyclopædia Britannica, Inc.

About two-thirds of the air in the atmosphere is composed of the inert gas nitrogen. During breathing nitrogen is exhaled from the lungs chemically unchanged. Most nitrogen exists as a free element in the atmosphere. The compounds it forms are extremely active and essential to all living things.

Protoplasm in living cells requires nitrogen for its formation. Protein, which is essential to life, is composed of nitrogen compounds linked together. Despite the abundance of free nitrogen in the air, it must be combined in compounds to be used by living things. The process by which free nitrogen is joined to other elements is called nitrogen fixation.

Natural Fixation and Circulation of Nitrogen

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Nitrogen fixation occurs in nature by the actions of lightning and bacteria. A flash of lightning unites nitrogen with oxygen to form nitric oxide (NO), which changes to nitrogen dioxide (NO2) upon cooling. Nitrogen dioxide combines with water to form nitric acid (HNO3). The dilute acid falls to the earth and reacts with minerals in the soil to produce nitrates. The nitrates form compounds necessary for cell growth. A greater amount of nitrogen is fixed by the action of bacteria in the soil and plant roots.

Among nitrogen-fixing bacteria are Clostridium pasteurianum and species of the genera Azotobacter and Rhizobium. Plant-dwelling bacteria live only on the roots of legumes. However, they fix more nitrogen than these plants require. The surplus is stored in the roots and escapes to the soil when the plant dies. Both soil and plant-dwelling bacteria take nitrogen from the air and combine it with hydrogen to form compounds that join to form proteins.

Nitrogen in living tissues can be used repeatedly. If a plant or animal dies, bacteria of decay break up proteins, and nitrogen is released in ammonia (NH3). Part of this escapes into the air. The remainder is acted upon by another type of bacteria to convert ammonia to nitrites. Still another type of bacteria changes the nitrites to nitrates, which plants use to create proteins. The bacteria that do this vital work are called nitrifying bacteria. The opposite result is produced by denitrifying bacteria. They act on protein during the decay process to release nitrogen to the atmosphere. This continual loss is made up, in part, by the action of the nitrifying bacteria. The circulation of nitrogen between the atmosphere and the soil is called the nitrogen cycle.

Artificial Fixation of Nitrogen

When plants die they return nitrogen to the soil. When crops are harvested, however, nitrogen is removed and is not returned. For this reason, it is necessary to cover the soil periodically with nitrogen compounds called fertilizers. Sodium nitrate, ammonium sulfate, and the waste products of animals are substances that provide the soil with nitrogen.

Natural processes do not produce the necessary amounts of such nitrogen compounds. Chemists have devised a number of processes for converting free nitrogen into usable nitrogen compounds. The Haber-Bosch process subjects a mixture of nitrogen and hydrogen to tremendous pressure in the presence of an iron catalyst. The gases unite to form ammonia. This is the most widely used industrial method of nitrogen fixation. The Casale process and the Claude process are variations of the Haber-Bosch method.

A second important method is the electric arc process. In this process, air is blown through an electric furnace. Nitrogen and oxygen unite to form nitrogen peroxide which is then passed through a spray of water to form nitric acid. This method requires a large supply of low-cost electric power. In the cyanamide process, nitrogen is passed over hot calcium carbide (CaC2). The resulting reaction produces calcium cyanamide (CaCN2). This compound can be used directly as a fertilizer or can be converted to ammonia.

Chemistry of Nitrogen

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Nitrogen was first identified by the British chemist Daniel Rutherford in 1772. It is a colorless gas at standard temperature and has an atomic weight of 14.0067. It liquefies at –195.8 °C (–320.4 °F) and freezes at –209.9 °C (–345.8 °F). The valence of nitrogen ranges from one to five. These combinations are illustrated by its compounds with divalent oxygen. It forms nitrous oxide (N2O), nitric oxide (NO), nitrogen trioxide (N2O3), nitrogen dioxide (NO2) and nitrogen pentoxide (N2O5). In most cases, however, the valence of nitrogen in its compounds is three or five.

Compounds of Nitrogen

The two most familiar nitrogen compounds are nitric acid and ammonia, a base. Students find many uses for these reagents in their chemistry courses. Nitrogen combines with metallic elements such as magnesium to form magnesium nitride (Mg3N2). Nitrides react with water to yield ammonia. Carbon and nitrogen unite and act as a radical (–CN) called the cyanide radical. The cyanide radical combines with hydrogen, potassium, or sodium to form cyanides. These compounds are poisonous but have important commercial uses.

Nitrogen is relatively inactive chemically and is slow to form compounds. Thus it is not surprising to find that most nitrogen compounds are unstable. Many break down or decompose with explosive violence. It is this characteristic that explains why many commonly used explosives are nitrogen compounds. The nitrogen compound hydrazine is one of the most powerful fuels. It is a member of a family of nitrogen compounds called hydronitrogens that are analogous to the hydrocarbons.

The most important organic compounds of nitrogen are the proteins. These are complicated molecules built from the amino acids, in which the amino group (–NH2) is the basic structural unit. The aniline dyes, which contain nitrogen, have a special affinity for the proteins in silk and wool fabrics. Most photographic developers contain nitrogen. Drugs such as caffeine, quinine, and morphine are also valuable nitrogen compounds (seechemistry).

Element Properties

Symbol

N

Atomic number

7

Atomic weight

14.0067

Group in periodic table

15 (Va)

Boiling point

–320.4 °F (–195.8 °C)

Melting point

–345.8 °F (–209.9 °C)

Specific gravity

0.00125

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